Reactive azo dyes, method for the production and use thereof

ABSTRACT

Reactive azo dyes, preparation thereof and use thereof  
     The present invention relates to reactive dyes of the general formula (1)  
                 
 
     where X 1 , X 2 , R, M, m and n are each as defined in claim 1, processes for their preparation and also their use for dyeing and printing hydroxyl- and/or carboxamido-containing materials.

[0001] Reactive azo dyes, preparation thereof and use thereof.

[0002] The present invention relates to the field of fiber-reactivedyes.

[0003] DE-A-4434989, DE 19600765, DE 19810906 and EP-A 922735 disclosedyes which are structurally similar to the hereinbelow described dyes ofthe present invention, but which differ with regard to the reactivegroup or in the type of coupling component. These known dyes have anumber of technical disadvantages in the dyeing of textile materials.

[0004] It is an object of the present invention to ameliorate thesetechnical disadvantages.

[0005] It has now been found that, surprisingly, the hereinbelowdescribed dyes of the general formula (1) are advantageous over theknown dyes:

[0006] The present invention accordingly provides reactive dyes of thegeneral formula (1)

[0007] where

[0008] R is hydrogen, alkyl or substituted alkyl

[0009] X¹ is halogen, amino, optionally substituted amino or X²,

[0010] X² is a substituent of the general formula (2)

[0011]  where

[0012] R¹ is substituted or unsubstituted aryl,

[0013] B is alkylene which may be interrupted by an oxygen atom, and

[0014] R² is a —SO₂CH═CH₂ or —SO₂CH₂CH₂Z radical, where Z is a moietywhich can be eliminated by the action of alkali,

[0015] n and m are each 0 or 1, and

[0016] M is hydrogen, ammonium, an alkali metal or the equivalent of analkaline earth metal.

[0017] In the general formula (1), an alkali metal M can be inparticular lithium, sodium and potassium, whereas the alkaline earthmetal is calcium in particular. Preferably, M is hydrogen or sodium.

[0018] Halogen X¹ is in particular fluorine or chlorine, and substitutedamino denotes in particular amino which is substituted by an arylradical bearing one or more fiber-reactive radicals —SO₂CH═CH₂ or—SO₂CH₂CH₂Z′, where Z′ represents a moiety which can be eliminated bythe action of alkali. Preferably, amino is substituted bym-sulfatoethylsulfonylphenyl or p-sulfatoethylsulfonylphenyl.

[0019] Alkyl R is preferably (C₁-C₈)-alkyl and particularly preferably(C₁-C₄)-alkyl. Examples of alkyl groups of this type are methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl. Alkyl Rcan be substituted by an SO₃H group for example.

[0020] Aryl R¹ is in particular phenyl which can be mono- orpolysubstituted by for example (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, chlorine,fluorine or SO₃H. Preferably, R¹ is phenyl or an aryl radical whichbears a sulfo group.

[0021] Alkylene B is preferably (C₁-C₈)-alkylene and particularlypreferably (C₁-C₄)-alkylene. Examples of alkylene groups of this typeare methylene, ethylene, n-propylene, i-propylene and butylene. Alkyleneinterrupted by an oxygen atom is preferably —(CH₂)₂—O—(CH₂)₂—.

[0022] Examples of Z radicals which can be eliminated by the action ofalkali, ie under dyeing conditions, are chlorine, bromine, sulfato,thiosulfato, phosphate, (C₂-C₅)— alkanoyloxy such as for exampleacetyloxy, benzoyloxy, sulfobenzoyloxy or p-toluylsulfonyloxy, of whichsulfato is preferred.

[0023] The groups “sulfato”, “thiosulfato” and “phosphate” include notonly their acid form but also their salt form. Accordingly, thiosulfatogroups conform to the general formula —S—SO₃M, phosphato groups conformto the general formula —OPO₃M₂ and sulfato groups conform to the generalformula —OSO₃M, in each of which M is as defined above.

[0024] Preferred reactive dyes of the present invention are those of thegeneral formula (1) where the radical of the general formula (2)corresponds to one of the radicals (2-1) to (2-4)

[0025] where M is as defined above.

[0026] Particular preference is given to the dyes of the formulae (1a)to (1c) according to the invention

[0027] where M, n and X¹ are each as defined above.

[0028] The reactive dyes of the general formula (1) according to theinvention are generally present as a preparation in solid or liquid(dissolved) form. In solid form, they generally contain the electrolytesalts customary in the case of water-soluble and especiallyfiber-reactive dyes, such as sodium chloride, potassium chloride andsodium sulfate, and can further contain the auxiliaries customary incommercial dyes, such as buffer substances capable of setting a pH inaqueous solution between 3 and 7, such as sodium acetate, sodium borate,sodium bicarbonate, sodium dihydrogenphosphate, sodium tricitrate anddisodium hydrogenphosphate, or small amounts of siccatives or, if theyare present in a liquid, aqueous solution (including the presence ofthickeners of the type customary in print pastes), they may also includesubstances which ensure a long life for these preparations, for examplemold preventatives.

[0029] The reactive dyes of the general formula (1) according to theinvention are preferably present as a dye powder or as a granular dyecontaining 10 to 80% by weight, based on the powder or granules, of anelectrolyte salt which is also known as a standardizing agent. Granulesin particular have particle sizes of 50 to 500 μm. These solidpreparations can further contain the aforementioned buffer substances ina total amount of up to 10% by weight, based on the preparation. Whenthe dyes are present in aqueous solution, the total dye content in theseaqueous solutions will be up to about 50% by weight, for example between5 and 50% by weight, and the electrolyte salt content in these aqueoussolutions will preferably be below 10% by weight, based on the aqueoussolution. The aqueous solutions (liquid preparations) can contain theaforementioned buffer substances generally in an amount of up to 10% byweight, preferably up to 2% by weight.

[0030] Reactive dyes of the general formula (1) according to theinvention may have the same chromophor but differ with regard to thefiber-reactive group R². More particularly, in the case of the samechromophor, R² can be firstly —SO₂CH═CH₂ and secondly —SO₂CH₂CH₂Z,particularly preferably β-sulfatoethylsulfonyl. The fraction of dye inthe vinylsulfonyl form can be up to about 30 mol %, based on therespective dye chromophor. Preferably, the fraction of vinylsulfonyl dyeto β-ethyl-substituted dye is in a molar ratio between 5:95 and 30:70.

[0031] The present invention further provides processes for preparingthe reactive dyes of the general formula (1).

[0032] These are obtainable for example when a compound of the generalformula (3)

[0033] where X¹, X², M and n are each as defined above, is diazotizedand reacted with a compound of the formula (4)

[0034] Alternatively, a compound of the general formula (5)

[0035] where R, M, m and n are each as defined above, can be condensedwith a halotriazine of the general formula (6)

[0036] where X¹ and X² are each as defined above and X³ is fluorine orchlorine.

[0037] The compound of the general formula (6) can in turn be obtainedfrom trifluorotriazine or trichlorotriazine and one or two compounds ofthe general formula (2′)

[0038] The compounds of the general formula (1), in which X² is aradical of the general formula (2), are alternatively also preparable byreaction of a compound of the general formula (5) with trihalotriazineand subsequent condensation with an amine of the general formula (2′).

[0039] Dyes of the general formula (1) where X¹ is X² and is not halogenare obtained by condensation of dyes of the general formula (1) where X¹is halogen by reaction with a reactive amine of the general formula (2′)in aqueous solution.

[0040] The compounds of the general formula (3) are obtainable invarious ways. When X² is a radical of the formula (2), the condensationproducts are obtained by reaction of halotriazines (6) withdiaminobenzenesulfonic acids or diaminobenzenedisulfonic acids,preferably 1,3-diaminobenzene-4-sulfonic acid,1,4-diaminobenzene-2-sulfonic acid and also1,4-diaminobenzene-2,5-disulfonic acid and2,4-diaminobenzene-1,5-disulfonic acid, or by condensation of atrichloro- or trifluorotriazine with diaminobenzenesulfonic acids ordiaminobenzenedisulfonic acids and subsequent condensation with an amineof the general formula (2′).

[0041] The abovementioned diazotization, coupling and condensationreactions are known per se to one skilled in the art and can be carriedout in the generally customary manner extensively described in thefield's literature.

[0042] The dyes of the general formula (1) according to the inventionare obtained as a solution or suspension in the above-described methodsof making and can be isolated by salting out. They can also be spraydried; another possibility is to evaporate the solution or suspension.

[0043] The reactive dyes of the general formula (1) according to theinvention possess useful application properties. They are used fordyeing and printing hydroxyl- and/or carboxamido-containing materials,for example in the form of sheetlike structures, such as paper andleather, or of films, of polyamide for example, or in bulk, as forexample polyamide and polyurethane, but especially in the form of fibersof the materials mentioned. Preferably, they are used for dyeing andprinting cellulosic fiber materials of any kind. They are also usefulfor dyeing and printing hydroxyl-containing fibers present in blendfabrics, for example blends of cotton with polyester fibers or polyamidefibers. It is also possible to use them to print textiles or paper bythe inkjet process.

[0044] The present invention accordingly also provides for the use ofthe reactive dyes of the general formula (1) according to the inventionfor dyeing and printing the materials mentioned or, to be more precise,processes for dyeing or printing such materials in a conventional mannerby using one or more reactive dyes of the general formula (1) accordingto the invention as a colorant.

[0045] Advantageously, the as-synthesized solutions of the reactive dyesof the general formula (1) according to the invention can be useddirectly as a liquid preparation for dyeing, if appropriate afteraddition of a buffer substance and similarly if appropriate afterconcentrating or diluting.

[0046] The materials mentioned are preferably used in the form of fibermaterials, especially in the form of textile fibers, such as wovens oryarns, as in the form of hanks or wound packages.

[0047] Hydroxyl-containing materials are those of natural or syntheticorigin, for example cellulose fiber materials or regenerated productsthereof and polyvinyl alcohols. Cellulose fiber materials are preferablycotton, but also other vegetable fibers, such as linen, hemp, jute andramie fibers. Regenerated cellulose fibers are for example stapleviscose and filament viscose.

[0048] Carboxamido-containing materials are for example synthetic andnatural polyamides and polyurethanes, especially in the form of fibers,for example wool and other animal hairs, silk, leather, nylon-6,6,nylon-6, nylon-11 and nylon-4.

[0049] The reactive dyes of the general formula (1) according to theinvention can be applied to and fixed on the substrates mentioned,especially the fiber materials mentioned, by the application techniquesknown for water-soluble dyes and especially by the applicationtechniques known for fiber-reactive dyes. Applied in this way by exhaustdyeing processes to cellulose fibers from a long liquor using a varietyof acid-binding agents with or without neutral salts, such as sodiumchloride or sodium sulfate, they produce dyeings having very good coloryields. They are preferably applied in an aqueous bath at temperaturesbetween 40 and 105° C., if appropriate at a temperature of up to 130° C.under pressure, and if appropriate in the presence of customary dyeingassistants. One possible procedure in this context is to introduce thematerial into the warm bath and to gradually heat the bath to thedesired dyeing temperature and to complete the dyeing operation at thattemperature. The neutral salts which speed the exhaustion of the dyesmay also, if appropriate, not be added to the bath until the actualdyeing temperature has been reached.

[0050] The padding process likewise provides excellent color yields andvery good color build-up on cellulose fibers, the dyes being fixable ina conventional manner by batching at room temperature or elevatedtemperature, for example at up to about 60° C., by steaming or using dryheat.

[0051] Similarly, the customary printing processes for cellulose fibers,which can be carried out either single-phase, for example by printingwith a print paste comprising sodium bicarbonate or some otheracid-binding agent and by subsequent steaming at 100 to 103° C., ortwo-phase, for example by printing with a neutral or weakly acidic printcolor and subsequent fixation either by passing the printed materialthrough a hot electrolyte-containing alkaline bath or by overpaddingwith an alkaline electrolyte-containing padding liquor with subsequentbatching or steaming or dry heat treatment of the alkali-overpaddedmaterial, produce strong prints having well-defined contours and a clearwhite ground. The outcome of the prints is substantially unaffected byvariations in the fixing conditions.

[0052] When fixing by means of dry heat in accordance with the customarythermofix processes, hot air from 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

[0053] The acid-binding agents which effect the fixation of the dyes onthe cellulose fibers include for example water-soluble basic salts ofthe alkali metals and likewise alkaline earth metals of inorganic ororganic acids or compounds which release alkali in the heat. Especiallysuitable are the alkali metal hydroxides and alkali metal salts of weakto medium inorganic or organic acids, the preferred alkali metalcompounds being the sodium and potassium compounds. Such acid-bindingagents include for example sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium bicarbonate, potassium carbonate, sodium formate,sodium dihydrogenphosphate, disodium hydrogenphosphate, sodiumtrichloroacetate, sodium silicate or trisodium phosphate.

[0054] The reactive dyes of the general formula (1) according to theinvention are notable for high reactivity, good fixability, very goodbuild-up and also high light and perspiration-light fastness. They cantherefore be used by the exhaust dyeing process at low dyeingtemperatures and require only short steaming times in pad-steamprocesses. The degrees of fixation are high, and the unfixed portionsare readily washed off, the difference between the degree of exhaustionand the degree of fixation being remarkably small, ie the hydrolysisloss being very small. They are also particularly useful for printing,especially on cotton, but also for printing nitrogenous fibers, forexample wool or silk or blend fabrics containing wool or silk.

[0055] The reactive dyes of the general formula (1) according to theinvention are further notable for the fact that, following the dyeingoperation, unfixed dye portions are very readily washed off the fibermaterial without adjacent whites in the washing operation being taintedby the dye which becomes detached. This is advantageous for the dyeoperation in that washing cycles and hence costs are saved.

[0056] The dyeings and prints prepared with the reactive dyes of thegeneral formula (1) according to the invention, especially on cellulosefiber materials, possess high color strength and high fiber-dye bondstability not only in the acidic but also in the alkaline range as wellas good lightfastness and very good wetfastness properties, such aswashing, water, seawater, crossdyeing and perspiration fastnesses, andalso good fastness to dry heat setting and pleating and to crocking.

[0057] The examples hereinbelow serve to illustrate the invention. Theparts and percentages are by weight, unless otherwise stated. Parts byweight relate to parts by volume as the kilogram relates to the liter.

[0058] The compounds described in the examples in terms of formulae areindicated in the form of the free acid. But generally they are preparedand isolated in the form of the alkali metal salts, such as lithium,sodium or potassium salts, and used for dyeing in the form of theirsalts. Similarly, the starting compounds and components indicated in theform of the free acid in the subsequent examples, especially tableexamples, can be used in the synthesis as such or in the form of theirsalts, preferably alkali metal salts.

[0059] The absorption maxima (λ_(max)) in the visible range reported forthe dyes according to the invention were determined on aqueous solutionsof their alkali metal salts.

EXAMPLE 1

[0060] 18.4 parts of 2,4,6-trichloro-1,3,5-triazine are suspended in 200parts of ice-water at 0-5° C. in the course of 30 minutes. 30.9 parts of2-(anilino)ethyl 2-sulfatoethyl sulfone are then added over 30 minuteswhile the reaction solution is maintained at pH 2.5 by concurrentmetered addition of 15% sodium carbonate solution. The reaction mixtureis subsequently stirred at 0-5° C., then mixed with 26.8 parts of1,4-diaminobenzene-2,5-disulfonic acid and adjusted to pH 5.5 with 15%sodium carbonate solution. The reaction mixture is subsequently warmedto 35° C. and subsequently stirred for 30 minutes. It is cooled to 10°C., admixed with 6.9 parts of sodium nitrite and added dropwise to aninitial charge of 100 parts of ice and 40 parts of conc. hydrochloricacid (31%). After stirring for 1 hour, excess nitrite is removed byaddition of sulfamic acid.

[0061] 23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid aredissolved in 300 parts of water and neutralized by addition of aqueoussodium hydroxide solution. The neutral solution is added dropwise to thecold diazotization batch at 10° C. over 30 minutes. The resulting pH is1.5-2.0. The pH is adjusted to 2.5 with 15% sodium carbonate solutionover 30 minutes and the solution is subsequently stirred at risingtemperature for 3 hours. It is then adjusted to pH 6 with sodiumcarbonate solution and buffered with NaH₂PO4/Na₂HPO₄. The solutionobtained is evaporated.

[0062] The dye obtained has the formula

[0063] It dyes and prints cotton in bluish red shades having goodfastnesses, especially high lightfastness.

[0064] The dyes of examples (2) to (32) were obtained in a similarmanner. To this end, the corresponding reactive amine was reacted withtrichlorotriazine and subsequently reacted with the condensationcomponent, diazotized and coupled onto the coupling component.Condensation Ex. Reactive amine component Coupling component Hue λmax 2) 2-(anilino)ethyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic  3) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid  4) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid  5) ″ ″ 7-amino-1-hydroxy- red 521naphthalene-3,6-disulfonic acid  6) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid  7) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 517naphthalene-3-sulfonic acid  8) ″ ″ 7-amino-1-hydroxy- red 524naphthalene-3,6-disulfonic acid  9) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 10) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 11)3-(anilino)propyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 12) ″ ″ 7-amino-1-hydroxy- red 527naphthalene-3,6-disulfonic acid 13) ″ ″ 7-sulfomethylamino- red 5371-hydroxynaphthalene- 3-sulfonic acid 14) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 15) ″ ″ 7-amino-1-hydroxy- red 521naphthalene-3,6-disulfonic acid 16) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 17) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 18) ″ ″ 7-amino-1-hydroxy- red 524naphthalene-3,6-disulfonic acid 19) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 20) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 21)2-(4-sulfophenyl-amino)ethyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 523naphthalene-3-sulfonic acid 22) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 23) ″ ″ 7-sulfomethylamino- red 5371-hydroxynaphthalene- 3-sulfonic acid 24) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 25) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 26) ″ ″ 7-sulfomethylamino- red 5311-hydroxynaphthalene- 3-sulfonic acid 27) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 517naphthalene-3-sulfonic acid 28) ″ 1,4-diaminobenzene-2-sulfonic acid7-amino-1-hydroxy- red 525 naphthalene-3,6-disulfonic acid 29) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 511naphthalene-3-sulfonic acid 30) ″ ″ 7-amino-1-hydroxy- red 515naphthalene-3,6-disulfonic acid 31) 3-(4-sulfophenyl-amino)propyl2-sulfatoethyl sulfone 1,4-diaminobenzene-2,5-disulfonic acid7-amino-1-hydroxy- red 524 naphthalene-3-sulfonic acid 32) ″ ″7-amino-1-hydroxy- red 528 naphthalene-3,6-disulfonic acid 33) ″ ″7-sulfomethylamino- red 537 1-hydroxy-naphthalene- 3-sulfonic acid 34) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 35) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 36) ″ ″ 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 37) ″1,4-diaminobenzene-2-sulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 38) ″ ″ 7-amino-1-hydroxy- red 523naphthalene-3,6-disulfonic acid 39) ″ 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 40) ″ ″7-amino-1-hydroxy- red 515 naphthalene-3,6-disulfonic acid

EXAMPLE 41

[0065] 21.8 parts of 4-nitroaniline-2-sulfonic acid are suspended in 400parts of water and neutralized with aqueous sodium hydroxide solution.6.9 parts of sodium nitrite are added, and the suspension is stirreduntil everything has dissolved.

[0066] The solution is added dropwise at 0-5° C. to initially charged100 parts of ice and 30 parts of conc. hydrochloric acid (31%) followedby stirring for 60 minutes. Excess nitrite is removed by addition ofsulfamic acid.

[0067] 31.9 parts of 7-amino-1-hydroxynaphthalene-3,6-disulfonic acidare dissolved in 300 parts of water and neutralized with aqueous sodiumhydroxide solution and added dropwise to the suspension of the diazoniumsalt over 30 minutes. The reaction mixture is gradually adjusted to pH 2with sodium carbonate solution and subsequently stirred for 1 hour. Thisaffords a dye solution which in the form of the free acid contains acompound of the formula (7)

[0068] The solution of the compound (7) is adjusted to pH 8.5 withaqueous sodium hydroxide solution and heated to 70° C. A solution of 5.6parts of NaHS in 50 parts of water is added dropwise and stirred in for30 minutes.

[0069] The compound obtained is precipitated by addition of 150 parts ofsodium chloride, filtered off and washed with aqueous sodium chloridesolution. The compound obtained conforms in the form of its free acid tothe formula (8)

[0070] 51.9 parts of compound (8) are dissolved in 500 parts of water.18.4 parts of 2,4,6-trichloro-1,3,5-triazine are suspended in 200 partsof ice-water at 0-5° C. in the course of 30 minutes. 30.9 parts of2-(anilino)ethyl 2-sulfatoethyl sulfone are then added over 30 minuteswhile the reaction solution is maintained at pH 2.5 by concurrentmetered addition of 15% sodium carbonate solution. The reaction mixtureis subsequently stirred at 0-5° C. for 1 hour, and the suspensionobtained is added to the solution of compound (8). The reaction mixtureis adjusted to pH 6 with sodium carbonate solution and warmed to 35° C.It is subsequently stirred for 1 hour. The end point of the reaction isdetermined by thin layer chromatography. The dye of example 6 isprecipitated by addition of potassium chloride, filtered off and dried.

[0071] The dye dyes cotton in a bluish red shade.

[0072] The compounds of examples 5), 13) and 14) are preparable in asimilar manner by condensing compound (8) with appropriate triazinederivatives.

[0073] By varying the coupling component in compound (8), it is possibleto prepare compounds of the general formula (5) by the above-describedmethod. These compounds can be converted into dyes of the generalformula (1) by reaction with appropriate triazine derivatives.

Example 42

[0074] 51.9 parts of compound (12) are dissolved in 500 parts of water,admixed with 4.2 parts of sodium fluoride and cooled to 5° C. 13.5 partsof 2,4,6-trifluorotriazine are then added. The pH initially decreasesbefore it adjusts to about 4-4.5. The reaction solution is subsequentlystirred for 15 minutes.

[0075] The reaction solution is then admixed with a neutral aqueoussolution of 40.3 parts of 3-(4-sulfophenylamino)propyl 2-sulfatoethylsulfone added dropwise, allowed to warm to 25° C. and all the whilemaintained at a pH of 6-6.5 kept constant by addition of sodiumcarbonate solution.

[0076] The end point of the reaction is determined by thin layerchromatography.

[0077] The solution is evaporated to leave a dye of the formula in theform of the free acid (9)

[0078] The dye dyes cotton in a bluish red shade.

[0079] The compounds of examples 43) to 49) are preparable in a similarmanner by the process described above. Coupling component in Ex.Reactive amine compound of formula (12) Hue λmax 43)3-(4-sulfophenylamino)propyl 7-amino-1-hydroxynaphthalene- red 5182-sulfatoethyl sulfone 3-sulfonic acid 44) 2-(4-sulfophenylamino)ethyl2-sulfatoethyl sulfone 7-amino-1-hydroxynaphthalene- red 5253,6-disulfonic acid 45) ″ 7-amino-1-hydroxynaphthalene- red 5183-sulfonic acid 46) 2-(anilino)ethyl 2-sulfatoethyl sulfone7-amino-1-hydroxynaphthalene- red 524 3,6-disulfonic acid 47) ″7-amino-1-hydroxynaphthalene- red 519 3-sulfonic acid 47)3-(anilino)propyl 2-sulfatoethyl sulfone 7-amino-1-hydroxynaphthalene-red 524 3,6-disulfonic acid 48) ″ 7-amino-1-hydroxynaphthalene- red 5183-sulfonic acid

EXAMPLE 49

[0080] 32.3 parts of 3-(anilino)propyl 2-sulfatoethyl sulfone aredissolved in 200 parts of water at pH 5 by addition of 15% sodiumcarbonate solution and admixed with 4.6 parts of sodium fluoride. Aftercooling to 0° C., the solution is admixed with 13.5 parts of2,4,6-trifluorotriazine. The pH initially decreases and then adjusts to3.5-4.0. The reaction mixture is subsequently stirred for 15 minutes.18.8 parts of 2,4-diaminobenzene-1,5-disulfonic acid are then added, thepH is adjusted to 5.5 with sodium carbonate solution and the solution isallowed to warm to 20-25° C. After stirring for 1 hour, 6.9 parts ofsodium nitrite are added. The solution is then transferred over 30minutes into an initial charge of 100 parts of ice and 50 parts of conc.hydrochloric acid (31%). The solution is subsequently stirred for 1hour, and excess nitrite is then removed by addition of sulfamic acid.

[0081] 23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulfonic acid aredissolved in 300 parts of water at neutral pH and by addition of aqueoussodium hydroxide solution. After heating to 50° C., 13.4 parts of thesodium salt of formaldehyde bisulfite are added. The solution issubsequently stirred for 30 minutes, cooled to 20° C. and added dropwiseinto the cold diazo solution at 10° C. The resulting pH is 1.5-2. The pHis adjusted to 2-2.5 with sodium carbonate solution and the mixture issubsequently stirred at rising temperature for 3 h. The solution isadjusted to pH 6 with sodium carbonate solution, buffered withNaH₂PO4/Na₂HPO₄ and evaporated. This affords a dye of the formula

[0082] The dye dyes cotton in a bluish red shade.

[0083] The dyes of examples 50) to 80), which are recited in the tablewhich follows, and also the dyes of examples 42) to 48) are preparablein a similar manner by having a reactive amine starting materialcondensed with trifluorotriazine, condensed with the appropriatecondensation component, diazotized and coupled onto the appropriatecoupling component. Condensation Ex. Reactive amine component Couplingcomponent Hue λmax 50) 3-(anilino)propyl 2-sulfatoethyl sulfone2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 518naphthalene-3-sulfonic acid 51) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 52) ″ ″ 7-sulfomethylamino- red 5351-hydroxynaphthalene- 3-sulfonic acid 53) ″1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 525naphthalene-3-sulfonic acid 54) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 55) ″ 1,3-diaminobenezene-4-sulfonicacid 7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 56) ″ ″7-amino-1-hydroxy- red 514 naphthalene-3,6-disulfonic acid 57)2-(anilino)ethyl 2-sulfatoethyl sulfone2,4-diaminobenzene-1,5-disulfonic acid 7-sulfomethylamino- red 5321-hydroxynaphthalene- 3-sulfonic acid 58) ″ ″ 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 59) ″ ″ 7-amino-1-hydroxy- red 523naphthalene-3,6-disulfonic acid 60) ″ 1,4-diaminobenzene-2,5-disulfonicacid 7-sulfomethylamino- red 536 1-hydroxynaphthalene-3- sulfonic acid61) ″ ″ 7-amino-1-hydroxy- red 525 naphthalene-3-sulfonic acid 62) ″ ″7-amino-1-hydroxy- red 528 naphthalene-3,6-disulfonic acid 63) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 510naphthalene-3-sulfonic acid 64) ″ ″ 7-amino-1-hydroxy- red 514naphthalene-3,6-disulfonic acid 65) 2-(4-sulfophenyl-amino)ethyl2-sulfatoethyl sulfone 2,4-diaminobenzene-1,5-disulfonic acid7-amino-1-hydroxy- red 518 naphthalene-3-sulfonic acid 66) ″ ″7-amino-1-hydroxy- red 521 naphthalene-3,6-disulfonic acid 67) ″ ″7-sulfomethylamino- red 532 1-hydroxynaphthalene- 3-sulfonic acid 68) ″1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 69) ″ ″ 7-amino-1-hydroxy- red 528naphthalene-3,6-disulfonic acid 70) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid 71) 2-(4-sulfophenyl-amino)ethyl2-sulfatoethyl sulfone 1,3-diaminobenzene-4-sulfonic acid7-amino-1-hydroxy- red 510 naphthalene-3-sulfonic acid 72) ″ ″7-amino-1-hydroxy- red 515 naphthalene-3,6-disulfonic acid 73)3-(4-sulfophenyl-amino)propyl 2-sulfatoethyl sulfone1,4-diaminobenzene-2,5-disulfonic acid 7-amino-1-hydroxy- red 524naphthalene-3-sulfonic acid 74) ″ ″ 7-amino-1-hydroxy- red 527naphthalene-3,6-disulfonic acid 75) ″ ″ 7-sulfomethylamino- red 5361-hydroxynaphthalene- 3-sulfonic acid 76) ″2,4-diaminobenzene-1,5-disulfonic acid 7-amino-1-hydroxy- red 519naphthalene-3-sulfonic acid 77) ″ ″ 7-amino-1-hydroxy- red 522naphthalene-3,6-disulfonic acid 78) ″ ″ 7-sulfomethylamino- red 5311-hydroxynaphthalene- 3-sulfonic acid 79) ″1,3-diaminobenzene-4-sulfonic acid 7-amino-1-hydroxy- red 511naphthalene-3-sulfonic acid 80) ″ ″ 7-amino-1-hydroxy- red 515naphthalene-3,6-disulfonic acid

Example 81

[0084] 28.1 parts of 4-(2′-sulfatoethylsulfonyl)aniline are dissolved in250 parts of water by neutralization with 15% sodium carbonate solution.Parts of the dye of example 8) are introduced into the solution and thepH is adjusted to 5.5-6. After heating to 80° C., the pH is maintainedin the adjusted range by adding sodium carbonate solution. The course ofthe reaction is monitored by thin layer chromatography. After thereaction has ended, the dye solution is cooled down, buffered and dried.This affords a powder whose structure conforms to the formula

[0085] It dyes cotton in a bluish red shade having good fastnesses,especially high lightfastness.

[0086] Examples 82) to 88) indicated in the table which follows areobtained in a similar manner by using the dyes of the indicated examplesas a reactant and condensing them with a reactive amine. Starting dyeEx. example Reactive amine Hue λmax 82)  8)4-(2′-sulfatoethylsulfonyl)-N-ethylaniline red 527 83)  3)3-(2′-sulfatoethylsulfonyl)aniline red 536 84) 40)4-(2′-sulfatoethylsulfonyl)aniline red 516 85) 26)3-(2′-sulfatoethylsulfonyl)aniline red 533 86) 17) 2-(anilino)ethyl2-sulfatoethyl sulfone red 520 87)  8) 2-(anilino)propyl 2-sulfatoethylsulfone red 528 88) 26) 4-(2′-sulfatoethylsulfonyl)aniline red 533

1. A reactive dye of the general formula (1)

where R is hydrogen, alkyl or substituted alkyl, X¹ is halogen, amino,optionally substituted amino or X², X² is a substituent of the generalformula (2)

 where R¹ is substituted or unsubstituted aryl, B is alkylene which maybe interrupted by an oxygen atom, and R² is a —SO₂CH═CH₂ or —SO₂CH₂CH₂Zradical, where Z is a moiety which can be eliminated by the action ofalkali, n and m are each 0 or 1, and M is hydrogen, ammonium, an alkalimetal or the equivalent of an alkaline earth metal.
 2. A reactive dye asclaimed in claim 1, wherein n is
 1. 3. A reactive dye as claimed inclaim 1, conforming to one of the formulae (1a) to (1c):

where M, n and X¹ are each as defined in claim
 1. 4. A reactive dye asclaimed in claim 1, wherein M is hydrogen or sodium.
 5. A process forpreparing a reactive dye as claimed in claim 1, which comprisesdiazotizing and reacting a reactive amine component of the generalformula (3)

where X¹, X², M and n are each as defined in claim 1, with a compound ofthe formula (4)


6. A process for preparing a reactive dye of the general formula (I) asclaimed in claim 1, where X²is a radical of the general formula (2),which comprises reacting a compound of the general formula (5)

with a trihalotriazine and subsequent condensation with an amine of thegeneral formula (2′)


7. cancelled
 8. A process of dyeing or printing hydroxyl- and/orcarboxamido-containing material which comprises contacting the dye asclaimed in claim 1 with the material.
 9. The process as claimed in claim8, wherein the material is a fiber material.